Constructing Heterogeneous Interface by Growth of Carbon Nanotubes on the Surface of MoB2 for Boosting Hydrogen Evolution Reaction in a Wide pH Range.

Transition metal diborides represented by MoB2 have attracted widespread attention for their excellent acidic hydrogen evolution reaction (HER). Nevertheless, their electrocatalytic performance is generally unsatisfactory in high-pH electrolytes. Heterogeneous interface engineering is one of the most promising methods for optimizing the composition and structure of electrocatalysts, thereby greatly affecting their electrochemical performance. Herein, a heterostructure, composed of MoB2 and carbon nanotubes (CNTs), is rationally constructed by boronizing precursors including (NH4 )4 [NiH6 Mo6 O24 ]·5H2 O (NiMo6 ) and Co complexes on the carbon cloth (Co,Ni-MoB2 @CNT/CC). In this method, NiMo6 is boronized to form MoB2 by a modified molten-salt-assisted borothermal reduction. Meanwhile, Co catalyzes extra carbon sources to grow CNTs on the surface of MoB2 . Thanks to the successful production of the heterostructure, Co,Ni-MoB2 @CNT/CC exhibits remarkable HER performance with a low overpotential of 98.6, 113.0, and 73.9 mV at 10 mA cm-2 in acidic, neutral, and alkaline electrolytes, respectively. Notably, even at 500 mA cm-2 , the electrochemical activity of Co,Ni-MoB2 @CNT/CC exceeds that of Pt/C/CC in an alkaline solution and maintains over 50 h. Theoretical calculations reveal that the construction of the heterostructure is beneficial to both water dissociation and reactive intermediate adsorption, resulting in superior alkaline HER performance.

Continuous Ultrathin Zwitterionic Covalent Organic Framework Membrane Via Surface-Initiated Polymerization Toward Superior Water Retention.

Efficient construction of proton transport channels in proton exchange membranes maintaining conductivity under varied humidity is critical for the development of fuel cells. Covalent organic frameworks (COFs) hold great potential in providing precise and fast ion transport channels. However, the preparation of continuous free-standing COF membranes retaining their inherent structural advantages to realize excellent proton conduction performance is a major challenge. Herein, a zwitterionic COF material bearing positive ammonium ions and negative sulphonic acid ions is developed. Free-standing COF membrane with adjustable thickness is constructed via surface-initiated polymerization of COF monomers. The porosity, continuity, and stability of the membranes are demonstrated via the transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM) characterization. The rigidity of the COF structure avoids swelling in aqueous solution, which improves the chemical stability of the proton exchange membranes and improves the performance stability. In the higher humidity range (50-90%), the prepared zwitterionic COF membrane exhibits superior capability in retaining the conductivity compared to COF membrane merely bearing sulphonic acid group. The established strategy shows the potential for the application of zwitterionic COF in the proton exchange membrane fuel cells.

Ionic Porous Aromatic Frameworks Embedding Polyoxometalates for Heterogeneous Catalysis.

Porous aromatic frameworks (PAFs) are highly promising functional porous solids known for their feasible amenability and extraordinary stability. When the framework was modified by ionic functional groups, these ionic PAFs (iPAFs) exhibited charged channels for adsorption, separation, and catalysis. However, the surface areas of ionic porous frameworks are usually lower than that of neutral frameworks, and their synthesis is limited by specific strategies and complex modification processes. To address these challenges, an intuitive route to construct ionic porous framework with high specific surface area was proposed. Herein, a multivariate ionic porous aromatic framework (MTV-iPAFs, named PAF-270) was synthesized using readily available building units with ionic functional groups through a multivariable synthesis strategy. PAF-270 exhibited hierarchical structure with the highest specific surface area among reported imidazolium-functionalized PAFs. Utilizing its physical and chemical properties, the availability for polyoxometalate loading and heterogeneous catalysis of PAF-270 were explored. PAF-270 exhibited a high adsorption capacity up to 50 % for both H3O40PW12 (HPW) and (NH4)5H6PV8Mo4O40 (V8). HPW@PAF-270 and V8@PAF-270 exhibited excellent catalytic abilities for oleic acid esterification and extractive oxidative desulfurization, respectively. Due to the stability of PAFs, these materials also showed remarkable resistance to temperature and pH changes. Overall, these results underscore the potential application of MTV-iPAFs as versatile functional porous materials.

Rationally Designed Cyclooctatetrathiophene-Based Porous Aromatic Frameworks (COTh-PAFs) for Efficient Photocatalytic Hydrogen Peroxide Production.

Constructing stable and efficient photocatalysts for H2O2 production is of great importance and is challenging. In this study, the synthesis of three photoactive cyclooctatetrathiophene (COTh)-based porous aromatic frameworks (COTh-PAFs) in an alternating donor-acceptor (D-A) fashion is presented. In combination with a triazine-derived electron acceptor, PAF-363 exhibits high efficiency for the photosynthesis of H2O2 with production rates of 11733 µmol g-1 h-1(with sacrificial agent) and 3930 µmol g-1 h-1 (without sacrificial agent) from water and oxygen under visible light irradiation. Experimental results and theoretical calculations reveal that the charge transfer positions and the O2 adsorption sites in PAF-363 are both concentrated on COTh fragments, which facilitate the H2O2 production through the oxygen reduction reaction (ORR) pathway. This work highlights that the rational design of COTh-PAFs with consideration of D-A direction, charge transfer positions, and O2 adsorption sites provides a feasible access to efficient H2O2 production photocatalysts.

Boosting H+ Storage in Aqueous Zinc Ion Batteries via Integrating Redox-Active Sites into Hydrogen-Bonded Organic Frameworks with Strong π-π Stacking.

In the emerging aqueous zinc ion batteries (AZIBs), proton (H+ ) with the smallest molar mass and fast (de)coordination kinetics is considered as the most ideal charge carrier compared with Zn2+ counterpart, however, searching for new hosting materials for H+ storage is still at its infancy. Herein, redox-active hydrogen-bonded organic frameworks (HOFs) assembled from diaminotriazine moiety decorated hexaazatrinnphthalene (HOF-HATN) are for the first time developed as the stable cathode hosting material for boosting H+ storage in AZIBs. The unique integration of hydrogen-bonding networks and strong π-π stacking endow it rapid Grotthuss proton conduction, stable supramolecular structure and inclined H+ storage. As a consequence, HOF-HATN displays a high capacity (320 mAh g-1 at 0.05 A g-1 ) and robust cyclability of (>10000 cycles at 5 A g-1 ) based on three-step cation coordination storage. These findings get insight into the proton transport and storage behavior in HOFs and provide the molecular engineering strategy for constructing well-defined cathode hosting materials for rechargeable aqueous batteries.

Tuning Electron Delocalization of Redox-Active Porous Aromatic Framework for Low-Temperature Aqueous Zn-K Hybrid Batteries with Air Self-Chargeability.

Air self-charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self-charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low-temperature self-charging aqueous Zn-K hybrid ion batteries (AZKHBs) using a fully conjugated hexaazanonaphthalene (HATN)-based porous aromatic framework as the cathode material, exhibiting redox chemistry using K+ as charge carriers, and regulating Zn-ion solvation chemistry to guide uniform Zn plating/stripping. The unique AZKHBs exhibit the exceptional electrochemical properties in all-climate conditions. Most importantly, the large potential difference causes the AZKHBs discharged cathode to be oxidized using oxygen, thereby initiating a self-charging process in the absence of an external power source. Impressively, the air self-charging AZKHBs can achieve a maximum voltage of 1.15 V, an impressive discharge capacity (466.3 mAh g-1), and exceptional self-charging performance even at -40 °C. Therefore, the development of self-charging AZKHBs offers a solution to the limitations imposed by the absence of a power grid in harsh environments or remote areas.

Assembly-Dissociation-Reconstruction Synthesis of Covalent Organic Framework Membranes with High Continuity for Efficient CO2 Separation.

Covalent organic frameworks (COFs), at the forefront of porous materials, hold tremendous potential in membrane separation; however, achieving high continuity in COF membranes remains crucial for efficient gas separation. Here, we present a unique approach termed assembly-dissociation-reconstruction for fabricating COF membranes tailored for CO2/N2 separation. A parent COF is designed from two-node aldehyde and three-node amine monomers and dissociated to high-aspect-ratio nanosheets. Subsequently, COF nanosheets are orderly reconstructed into a crack-free membrane by surface reaction under water evaporation. The membrane exhibits high crystallinity, open pores and a strong affinity for CO2 adsorption over N2, resulting in CO2 permeance exceeding 1060 GPU and CO2/N2 selectivity surpassing 30.6. The efficacy of this strategy offers valuable guidance for the precise fabrication of gas-separation membranes.

Ultrathin Free-Standing Porous Aromatic Framework Membranes for Efficient Anion Transport.

Porous aromatic frameworks (PAFs) show promising potential in anionic conduction due to their high stability and customizable functionality. However, the insolubility of most PAFs presents a significant challenge in their processing into membranes and subsequent applications. In this study, continuous PAF membranes with adjustable thickness were successfully created using liquid-solid interfacial polymerization. The rigid backbone and the stable C-C coupling endow PAF membrane with superior chemical and dimensional stabilities over most conventional polymer membranes. Different quaternary ammonium functionalities were anchored to the backbone through flexible alkyl chains with tunable length. The optimal PAF membrane exhibited an OH- conductivity of 356.6 mS ⋅ cm-1 at 80 °C and 98 % relative humidity. Additionally, the PAF membrane exhibited outstanding alkaline stability, retaining 95 % of its OH- conductivity after 1000 hours in 1 M NaOH. To the best of our knowledge, this is the first application of PAF materials in anion exchange membranes, achieving the highest OH- conductivity and exceptional chemical/dimensional stability. This work provides the possibility for the potential of PAF materials in anionic conductive membranes.

A Bipyridyl Covalent Organic Framework with Coordinated Cu(I) for Membrane C3 H6 /C3 H8 Separation.

Covalent organic frameworks (COFs) mixed matrix membranes (MMMs) combining individual attributes of COFs and polymers are promising for gas separation. However, applying COF MMMs for propylene/propane (C3 H6 /C3 H8 ) separation remains a big challenge due to COF inert pores and C3 H6 /C3 H8 similar molecular sizes. Herein, the designed synthesis of a Cu(I) coordinated COF for membrane C3 H6 /C3 H8 separation is reported. A platform COF is synthesized from 5,5'-diamino-2,2'-bipyridine and 2-hydroxybenzene-1,3,5-tricarbaldehyde. This COF possesses a porous 2D structure with high crystallinity. Cu(I) is coordinated to bipyridyl moieties in the COF framework, acting as recognizable sites for C3 H6 gas, as shown by the adsorption measurements. Cu(I) COF is blended with 6FDA-DAM polymer to yield MMMs. This COF MMM exhibits selective and permeable separation of C3 H6 from C3 H8 (C3 H6 permeability of 44.7 barrer, C3 H6 /C3 H8 selectivity of 28.1). The high porosity and Cu(I) species contribute to the great improvement of separation performance by virtue of 2.3-fold increase in permeability and 2.2-fold increase in selectivity compared to pure 6FDA-DAM. The superior performance to those of most relevant reported MMMs demonstrates that the Cu(I) coordinated COF is an excellent candidate material for C3 H6 separation membranes.

Single-Ion Polymer Electrolyte Based on Lithium-Rich Imidazole Anionic Porous Aromatic Framework for High Performance Lithium-Ion Batteries.

The low ionic conductivity and Li+ transference number ( t L i + ${t}_{L{i}^ + }$ ) of solid polymer electrolytes (SPEs) seriously hinder their application in lithium-ion batteries (LIBs). In this study, a novel single-ion lithium-rich imidazole anionic porous aromatic framework (PAF-220-Li) is designed. The abundant pores in PAF-220-Li are conducive to the Li+ transfer. Imidazole anion has low binding force with Li+ . The conjugation of imidazole and benzene ring can further reduce the binding energy between Li+ and anions. Thus, only Li+ moved freely in the SPEs, remarkably reducing the concentration polarization and inhibiting lithium dendrite growth. PAF-220-quasi-solid polymer electrolyte (PAF-220-QSPE) is prepared through solution casting of Bis(trifluoromethane)sulfonimide lithium (LiTFSI) infused PAF-220-Li and Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP), and possessed excellent electrochemical performance. The electrochemical property are further improved by preparing all-solid polymer electrolyte (PAF-220-ASPE) via pressing-disc method, which has a high Li+ conductivity of 0.501 mS cm-1 and t L i + ${t}_{L{i}^ + }$ of 0.93. The discharge specific capacity at 0.2 C of Li//PAF-220-ASPE//LFP reached 164 mAh g-1 , and the capacity retention rate is 90% after 180 cycles. This study provided a promising strategy for SPE with single-ion PAFs to achieve high-performance solid-state LIBs.

Immobilizing Quinone-Fused Aza-Phenazine into π-d Conjugated Coordination Polymers with Multiple-Active Sites for Sodium-Ion Batteries.

The development of coordination polymers with π-d conjugation (CCPs) provides ide prospects for exploring the next generation of environmental-friendliness energy storage systems. Herein, the synthesis, experimental characterizations, and Na-ion storage mechanism of π-d CCPs with multiple-active sites are reported, which use quinone-fused aza-phenazine (AP) and aza-phenazin (AP) as the organic ligands coordinated with the metal center (Ni2+ ). Among them, NiQAP as the cathode material exhibits impressive electrochemical properties applied in sodium-ion batteries (SIBs), including the high initial/stable discharge specific capacities (180.0/225.6 mAh g-1 ) at 0.05 A g-1 , a long-term cycle stability up to 10,000 cycles at 1.0 A g-1 with a high reversible capacity of 100.1 mAh g-1 , and good rate capability of 99.6 mAh g-1 even at 5.0 A g-1 . Moreover, the Na-ion storage mechanism of NiQAP is also performed by the density functional theory (DFT) calculation, showing multiple-active sites of C≐O and C≐N (in the quinone and phenazine structure) and NiO4 (in the coordination unit) for Na-ion storage. These results highlight the importance of organic electrode material with the coordination units and provide a foundation for further studying the CCPs with multiple active sites for energy storage systems.

Isomerization of DASA Molecules in the Nanopores of Metal-Organic Frameworks: What Determines Its Reversibility?

In recent years, light-responsive molecules have been incorporated in metal-organic frameworks (MOFs) to fabricate light-responsive intelligent devices, where reversible isomerization of the guest molecules in the nanopores is crucial. However, how to design a porous environment of MOFs to achieve a reversible isomerization remains unknown until now. In this work, donor-acceptor Stenhouse adducts (DASAs), a new kind of visible light responsive compound, were confined in the nanopores of different MOFs to study their isomerization upon visible-light irradiation/mild heating. We found that the polarity of the pore environment is the key to control the reversibility of isomerization of such guest molecules. Under the guidance of this principle, MIL-53(Al) was screened to investigate the proton conductivity and switching performance of the DASA-confined MOF. The proton conductance was up to 0.013 S cm-1 at 80 °C and 98 % RH, and at least 30 switching cycles were achieved thanks to the Grotthuss-type mechanism and the low polarity of MIL-53(Al) pore environment.

Preparation of Trimetallic-Organic Framework Film Electrodes via Secondary Growth for Efficient Oxygen Evolution Reaction.

Metal-organic frameworks (MOFs) are promising electrocatalysts for clean energy conversion systems. However, developing MOF-based electrodes with high performance toward oxygen evolution reaction (OER) is still challenging. In this work, a series of MOF film electrodes derived from Ni-btz were prepared by employing the secondary growth strategy under solvothermal conditions. Fe and Co ions were also incorporated into the Ni-btz framework to produce a trimetallic coupling effect to obtain enhanced OER activity. The as-prepared FeCoNi-btz/NF exhibited not only good stability but also excellent OER performance under alkaline conditions. Furthermore, the possible intermediates including metal oxides and metal oxyhydroxides were confirmed by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).

Evaluating anti-viral effect of Tylvalosin tartrate on porcine reproductive and respiratory syndrome virus and analyzing the related gene regulation by transcriptomics.

BACKGROUND: Porcine reproductive and respiratory syndrome virus (PRRSV) is an economically important pathogen, characterized by its genetic and antigenic variation. The PRRSV vaccine is widely used, however, the unsatisfied heterologic protection and the risk of reverse virulence raise the requirement to find some new anti-PRRSV strategies for disease control. Tylvalosin tartrate is used to inhibit PRRSV in the field non-specifically, however, the mechanism is still less known. METHODS: The antiviral effects of Tylvalosin tartrates from three producers were evaluated in a cell inoculation model. Their safety and efficacy concentrations, and effecting stage during PRRSV infection were analyzed. And, the Tylvalosin tartrates regulated genes and pathways which are potentially related to the anti-viral effect were further explored by using transcriptomics analysis. Last, the transcription level of six anti-virus-related DEGs was selected to confirm by qPCR, and the expression level of HMOX1, a reported anti-PRRSV gene, was proved by western blot. RESULTS: The safety concentrations of Tylvalosin tartrates from three different producers were 40 µg/mL (Tyl A, Tyl B, and Tyl C) in MARC-145 cells and 20 µg/mL (Tyl A) or 40 µg/mL (Tyl B and Tyl C) in primary pulmonary alveolar macrophages (PAMs) respectively. Tylvalosin tartrate can inhibit PRRSV proliferation in a dose-dependent manner, causing more than 90% proliferation reduction at 40 µg/mL. But it shows no virucidal effect, and only achieves the antiviral effect via long-term action on the cells during the PRRSV proliferation. Furthermore, GO terms and KEGG pathway analysis was carried out based on the RNA sequencing and transcriptomic data. It was found that the Tylvalosin tartrates can regulate the signal transduction, proteolysis, and oxidation-reduction process, as well as some pathways such as protein digestion and absorption, PI3K-Akt signaling, FoxO signaling, and Ferroptosis pathways, which might relate to PRRSV proliferation or host innate immune response, but further studies still need to confirm it. Among them, six antivirus-related genes HMOX1, ATF3, FTH1, FTL, NR4A1, and CDKN1A were identified to be regulated by Tylvalosin tartrate, and the increased expression level of HMOX1 was further confirmed by western blot. CONCLUSIONS: Tylvalosin tartrate can inhibit PRRSV proliferation in vitro in a dose-dependent manner. The identified DEGs and pathways in transcriptomic data will provide valuable clues for further exploring the host cell restriction factors or anti-PRRSV target.

Covalent Organic Framework/g-C3N4 van der Waals Heterojunction toward H2 Production.

Photocatalytic water splitting into H2 is the most economic and environmentally friendly strategy for H2 production, and rationally constructing a heterojunction retains enormous influence on a photocatalytic system. Herein, 2D/2D covalent organic framework/graphitic carbon nitride (COF/CN) van der Waals heterojunctions were readily prepared via an ultrasonic method for high-efficiency visible-light photocatalytic H2 production. The photocatalytic H2 production performance of optimized COF/CN composites can reach up to 449.64 µmol·h-1, which is approximately 5 times that of pure CN (89.08 µmol·h-1). The characterization and experimental studies reveal that the synergistic effect between COF and CN contributes to promoting the interfacial migration and spatial separation of photoinduced e--h+ pairs, further boosting the photocatalytic hydrogen production activity. This work may open a new window to design and fabricate effective heterojunction photocatalysts for photocatalytic energy conversion.

Controlled Partial Linker Thermolysis in Metal-Organic Framework UiO-66-NH2 to Give a Single-Site Copper Photocatalyst for the Functionalization of Terminal Alkynes.

Metal-organic frameworks (MOFs) with expanding porosity and tailored pore environments are intriguing for catalytic applications. We report herein a straightforward method of controlled partial linker thermolysis to introduce desirable mesopores into mono-ligand MOFs, which is different from the classical thermolyzing method that starts from mixed-linker MOFs. UiO-66-NH2 , after partial ligand thermolysis, exhibits significant mesoporosity, retained crystal structure, improved charge photogeneration and abundant anchoring sites, which is ideal to explore single-site photocatalysis. Atomically dispersed Cu is then accommodated in the tailored pore. The resulting single-site Cu catalyst exhibits excellent performance for photocatalytic alkylation and oxidation coupling for the functionalization of terminal alkynes. The study highlights the advantage of controlled partial linker thermolysis to synthesize hierarchical MOFs to achieve the advanced single-site photocatalysis.

Ultramicroporous Covalent Organic Framework Nanosheets with Functionality Pair for Membrane C2 H2 /C2 H4 Separation.

Gas separation efficiency of covalent organic framework (COF) membrane can be greatly elevated through precise functionalization. A pair-functionalized COF membrane of 1,3,5-triformylphloroglucinol (TP) and isoquinoline-5,8-diamine (IQD) monomers in two and three nodes is designed and synthesized. TP-IQD is crystallized in a two-dimensional structure with a pore size of 6.5 Šand a surface area of 289 m2 g-1 . This COF possesses N-O paired groups which cooperatively interact with C2 H2 instead of C2 H4 . TP-IQD nanosheets of ≈10 µm in width and ≈4 nm in thickness are prepared by mechanical exfoliation; they are further processed with 6FDA-ODA polymer into a hybrid membrane. High porosity and functionality pair of TP-IQD offer the membrane with significantly increased C2 H2 permeability and C2 H2 /C2 H4 selectivity which are 160 % and 430 % higher of pure 6FDA-ODA. The boosted performance demonstrates high efficiency of the pair-functionality strategy for the synthesis of separation-led COFs.

Porous Cyclodextrin Polymer Enables Dendrite-Free and Ultra-Long Life Solid-State Zn-I2 Batteries.

Zn-I2 batteries have attracted attention due to their low cost, safety, and environmental friendliness. However, their performance is still limited by the irreversible growth of Zn dendrites, hydrogen evolution reactions, corrosion, and shuttle effect of polyiodide. In this work, we have prepared a new porous polymer (CD-Si) by nucleophilic reaction of ß-cyclodextrin with SiCl4 , and CD-Si is applied to the solid polymer electrolyte (denoted PEO/PVDF/CD-Si) to solve above-mentioned problems. Through the anchoring of the CD-Si, a conductive network with dual transmission channels was successfully constructed. Due to the non-covalent anchoring effect, the ionic conductivity of the solid polymer electrolytes (SPE) can reach 1.64×10-3  S cm-1 at 25 °C. The assembled symmetrical batteries can achieve highly reversible dendrite-free galvanizing/stripping (stable cycling for 7500 h at 5 mA cm-2 and 1200 h at 20 mA cm-2 ). The solid-state Zn-I2 battery shows an ultra-long life of over 35,000 cycles at 2 A g-1 . Molecular dynamics simulations are performed to elucidate the working mechanism of CD-Si in the polymer matrix. This work provides a novel strategy towards solid electrolytes for Zn-I2 batteries.

Constructing Mechanical Shuttles in a Three-dimensional (3D) Porous Architecture for Selective Transport of Lithium Ions.

Lithium (Li) extraction from brines is a major barrier to the sustainable development of batteries and alloys; however, current separation technology suffers from a trade-off between ion selectivity and permeability. Herein, a crown ether mechanically interlocked 3D porous organic framework (Crown-POF) was prepared as the porous filler of thin-film nanocomposite membranes. Crown-POF with penta-coordinated (four Ocrown atoms and one Ntert-amine atom) adsorption sites enables a special recognition for Li+ ion. Moreover, the four Ntert-amine atoms on each POF branch facilitate the flipping motion of Li+ ion along the skeletal thread, while retaining the specified binding pattern. Accordingly, the crown ether interlocked POF network displays an ultrafast ion transfer rate, over 10 times that of the conventional porous materials. Notably, the nanocomposite membrane gives high speed and selectivity for Li+ ion transport as compared with other porous solid-based mixed-matrix membranes.

Crystallinity Regulation and Defects Passivation for Efficient and Stable Perovskite Solar Cells Using Fully Conjugated Porous Aromatic Frameworks.

Fully conjugated porous aromatic frameworks (PAFs) have been constructed through Gilch reaction. The obtained PAFs have rigid conjugated backbones, high specific surface area, and excellent stability. The prepared PAF-154 and PAF-155 have been successfully applied in the perovskite solar cells (PSCs) by doping into the perovskite layer. The champion PSC devices afford a power conversion efficiency of 22.8 % and 22.4 %. It is found that the PAFs can be used as an efficient nucleation template, thus regulating the perovskite crystallinity. Meanwhile, PAFs can also passivate defects and promote carriers transporting in the perovskite film. By the comparative study with their linear counterpart, we unravel that the efficacy of PAFs is highly related to their porous structure and rigid fully conjugated networks. The unencapsulated devices with PAFs doping exhibit outstanding long-term stability, retaining 80 % of their initial efficiencies after half-year storage in ambient conditions.